WO2002018699A1 - A nanometre-silver, long-acting, broad spectrum, antimicrobial, mouldproof granule and its producing methods - Google Patents

Abstract

The invention discloses a kind of nanometre-silver, long-acting, broad spectrum, antimicrobial, mouldproof granule and producing methods thereof, especially to modify the characteristic of multi-micropore nonmetal ore(silicate), particularly to let concavo-convex stick clay's surface and micropore adhere nanometer size silver, and confer it long-acting broad spectrum antimicrobial mouldproof property, that can be also used for producing plastics, ceramic, constructional material, rubber item and ornamental textiles. The invention has good antimicrobial property, broad antimicrobia spectrum, wide use, and the method is simple, operate easily.

Description

 Nano-silver long-acting broad-spectrum antibacterial cloud-proof particles and manufacturing method thereof

 The invention is a nano-silver long-acting broad-spectrum antibacterial mold-proof particle and a manufacturing method thereof, in particular to modify a non-metallic ore (silicate clay) having microporosity so as to have a broad-spectrum long-lasting antibacterial and antibacterial Mildew performance.

Background technique

 Generally, the housing environment and daily appliances do not have antibacterial, mildew and deodorizing effects, and the proliferation of microorganisms and bacteria in the living room, such as carpet syndrome, air conditioning syndrome, and pollution of electric water tanks, all affect people's physical and mental health. health. As people's health needs increase, antibacterial and anti-mildew functional products in various fields have emerged. For example, finishing antibacterial and anti-mildew functional finishing on textiles; adding antibacterial agents to plastics of household appliances or food containers to have antibacterial and anti-mildew properties; adding transition metal oxides to architectural coatings, allowing organic matter and microorganisms to interact with them It is oxidized or decomposed; antibacterial substances are added to the ceramic glaze layer to prevent the proliferation and growth of bacteria on the dark and damp sanitary ware.

 Chinese patent CN98126231. 7 discloses an antibacterial polymer material for home appliances, which is an antibacterial masterbatch comprising an antibacterial agent containing zeolite, zinc sulfate, zinc oxide, silver nitrate, polyethylene, and ethylene-vinyl acetate copolymer. However, the manufacturing method of this material is more complicated, and because of the poor compatibility and compatibility of zeolite and water, its application is limited. · Literatures on such silver-based antibacterial substances adsorbed by zeolites can also be found in US 5,900,258 and the like. Chinese patent 94118576. 1 proposes to chemically and physically treat the granules of the stems and cords of plants of the rush family to make the ultrafine silver firmly adhere to the surface of the granules. This method is not applicable because the carrier is granules of stems and stems of grasses, and therefore it is resistant to high temperatures, especially when applied to ceramics.

Summary of the Invention The purpose of the present invention is to overcome the shortcomings of the prior art, and to propose a long-acting broad-spectrum antibacterial mold-resistant granule with nano-silver and a method for manufacturing the same. , Architectural coatings, rubber products, etc., can also be applied to decorative textiles.

 The object of the present invention is achieved by the following technical solutions: selecting attapulgite clay

Attapulgi te (also known as Palygorski te in the literature) or similar pore-shaped silicate as a carrier, using its large number of micropores, through chemical and physical methods, introducing nanoscale into its micropores The silver-based antibacterial and anti-mold substance has a broad-spectrum antibacterial and anti-mold effect without changing the basic characteristics and uses of the attapulgite clay itself, and it can be applied to home appliance plastics, plastic films, architectural coatings, ceramics and rubber products. .

 According to the above technical solution, the present invention is characterized in that nano-level elements are attached to the surface and micropores of the attapulgite clay.

 According to the above technical solution, the present invention is also characterized by being manufactured according to the following proportions and manufacturing methods:

 Attapulgite clay 100-l OOOg

AgN0 ₃ 10-20g

NaOH: 1-3g, NH ₃ · H ₂ 0: 10-30ml, and also includes reducing agents such as formaldehyde or glucose or hydrogen peroxide.

When manufacturing, first react AgN0 ₃ with NaOH, then add Question _3. H ₂ 0 to form [Ag (NH ₃ ) ₂ ] ^{+ and} then put the attapulgite clay into it, maintaining the bath ratio 1: 10-20, after 1- After stirring for 2 hours, a colloidal solution was prepared, and a reducing agent was further added. At this time, metallic silver was precipitated on the surface and pores of the attapulgite clay. After baking, the surface of the metallic silver was oxidized to silver oxide Ag ₂ 0. Made by filtering, baking and crushing.

Reaction mechanism: Ag + + 2 legs ₃ → [Ag (NH ₃ ) ₂ ] ⁺ [Ag (NH ₃ ) ₂ ] ⁺ + reducing agent (C ₆ H ₁₂ 0 ₆ ) → kg

Ag oxidizes its surface to form Ag ₂ 0

Sterilization mechanism: Ag ₂ 0 + H ₂ 0 → 2Ag ⁺ + 20H—

In the presence of a trace amount of water, Ag ⁺ can easily complex with specific genes (such as -SH) in negatively charged bacterial proteins, so that the active enzymes that the bacteria depend on can lose their activity, thereby achieving the purpose of sterilization. Enzyme + 2H +

According to the classical theory, silver is a relatively stable substance, which is basically insoluble in water, and its own bactericidal power and antibacterial spectrum are neither so strong nor so broad. Only by miniaturizing the silver material scale, it can reach 10— ⁹ M nanoscale, make full use of its surface effect. Small size effect and use of broad language, strong antibacterial, good stability, not only does not weaken the effect of water, but enhanced characteristics and in the process of killing pathogenic bacteria, not affected by the pH of the human body and so on. Nano-silver technology is a product based on the three basic disciplines of quantum chemistry, materials chemistry, and biochemistry. By miniaturizing the material scale of silver, it is brought to the nanometer level. Due to the greatly increased surface area, the surface structure also changes greatly, the surface activity is greatly enhanced, and it exhibits a very high specific function. There are reports in the literature that, after detection, the MIC for pathogenic bacteria is 0.16 to 8.97 mg / ml, and the MBC is 3.05 to 81.97 mg / ml, and its bactericidal ability has been increased more than 200 times.

In order to realize nano-silver technology, the present invention selects attapulgite clay with a large number of micropores in the structure. According to literature reports, it is a layered chain magnesia silicate, and the crystal includes a large number of pores. The pores have a radius of 50-55A, and have special properties such as excellent adsorption, colloid and catalytic properties. Due to its Coulomb electrostatic force, it has strong adsorption on cations; at the same time, it also has strong cation exchange capacity. Therefore, silver ions can be adsorbed in their micropores and then reduced to silver by chemical reaction. Due to the limitation of the size of the micropores, the size of the elemental silver existing in the pores is also on the nanometer level, that is, on the nanometer level.

 Compared with the prior art, the present invention has the following significant features and significant improvements:

 1. The carrier attapulgite clay used is not only low in cost, convenient to mine, but also extremely abundant in China. More importantly, it makes full use of its good compatibility. It has been used as a filling material in plastics, rubber, coatings and ceramics. Features widely used in other fields can increase its antibacterial, anti-mildew and deodorizing effect without affecting the manufacturing process in the field.

 2. Due to the use of nanotechnology, the particles of the present invention have good antibacterial properties and a broad antibacterial spectrum, and have obvious killing effects on the following pathogenic bacteria and fungi.

 Pyrococcus: Staphylococcus aureus, Streptococcus type B, Pneumococcus, Meningococcus, Gonorrhea

 Enterobacteria: Escherichia coli, Shigella, Typhoid, Paratyphoid, Typhoid enterus, Enterobacter, Cholera suis, Proteus, Pneumoniae, Pseudomonas aeruginosa

 Pathogenic fungi: Candida albicans, Cryptococcus neoformans, Trichophyton gypsum, Trichophyton rubrum, Trichophyton rosacea, Trichophyton floccus, Trichophyton, Microcystis gypsum, Mucor, Aspergillus

 3. The manufacturing method of the present invention is simple and easy to operate.

4, a wide range of uses. Utilizing the properties of attapulgite clay as a filler, the modified clay particles of the present invention can be used in the fields of plastic products and films, rubber, coatings and ceramics without affecting Their performance.

 In the method of the present invention, the attapulgite clay as a carrier may be replaced by a pore-shaped silicate material such as bentonite, sepiolite, and diatomaceous earth. However, attapulgite clay is the best for producing antibacterial and antifungal effects.

Nie Jia embodiment of the present invention

 The following further describes the present invention in combination with the embodiments:

 Example 1.

Take 16 g of AgN0 ₃ , dissolve in 600 liters of water, add 2 g of NaOH, 250 ml of 26% NH ₃ H ₂ 0, and then add 100 g of 200-mesh powdered attapulgite clay, mix well, and stir at room temperature for 1.5 hours. Make it fully react with the solution in the front bath until the reaction solution is in the form of a colloid, take 60 ml of hydrogen peroxide, add it, and warm to 70 ° C to reduce the Ag ⁺ absorbed in the micropores of the attapulgite clay. All the solutions were filtered through a filtering device to obtain a viscous substance, which was baked and dried to obtain a block, and then pulverized to a 200-mesh powder.

 Example 2.

Take 20 grams of AgN0 ₃ , dissolve in 800 liters of water, add 1.6 grams of NaOH, add 30% of 26% NH ₃ H ₂ 0, and then add 500 grams of 300 mesh powdered attapulgite clay, mix well and stir at room temperature for 1.8 hours Make it fully react with the solution in the front bath until the reaction solution is in the form of a colloid. Take 3.4 ml of hydrogen peroxide, add it, and raise the temperature to 75 ° C to reduce the Ag + absorbed in the micropores of the attapulgite clay. All the solutions were filtered through a centrifugal filtration device to obtain a viscous substance, which was baked and dried to obtain a block, and then pulverized to a 200-mesh powder.

 Example 3.

Take 16 g of AgN0 ₃ , dissolve in 50 liters of water, add 1.6 g of NaOH, and add water to 800 liters. Add 26% NH ₃ H ₂ 0 25ml, and then add 1000 g of 200 mesh powdered attapulgite clay, mix well, and stir at room temperature for 2 hours to fully react with the solution in the front bath until the reaction solution appears In a colloidal form, 78 ml of glucose was taken and added thereto, and the temperature was raised to 70 ° C to reduce Ag ⁺ adsorbed in the micropores of the attapulgite clay. Then, all the solutions were filtered through a filtering device to obtain a viscous substance, which was baked and dried to obtain a lumpy substance, which was then divided into 200 mesh powders in 4 minutes.

 Example 4.

Take 16 grams of AgN0 ₃ , dissolve in 100 liters of water, add 1.6 grams of NaOH, add water to 500 liters, add 26% NH ₃ H ₂ 0 25 ml, and then add 800 grams of 200 mesh powdered attapulgite clay. Stir for 2 hours at room temperature to fully react with the solution in the front bath until the reaction solution is colloidal. Take 30 ml of formaldehyde, add to it, and warm to 78 ° C to adsorb it into the micropores of the attapulgite clay. Ag ⁺ is reduced. All the solutions were filtered through a centrifuge to obtain a viscous substance, which was baked and dried to obtain a block, and then pulverized to a 300-mesh powder.

Claims

 1. A nano-long-acting, broad-spectrum antibacterial and anti-mildew granule, which is characterized in that nano-scale element silver is attached to the surface and micropores of a non-metallic mineral silicate having micropores.  2. The nano-silver long-acting broad-spectrum antibacterial and anti-mold particle according to claim 1, characterized in that nano-scale elemental silver is attached to the surface and micropores of the attapulgite clay.  3. A method for manufacturing nano-silver long-acting broad-spectrum antibacterial mold-proof particles, which is characterized by the following proportions: Attapulgite clay 100-100 Og AgN0 ₃ 10- 20g NaOH: 1-3g, NH ₃ -H ₂ 0: 10-30ml, and also includes reducing agents such as formaldehyde or glucose or hydrogen peroxide.  The method of claim 3, wherein the manufacturing steps are: a. First react AgN0 ₃ with NaOH, and then add NH ₃ -H ₂ 0 to form [Ag (NH ₃ ) ₂ ] +; b. Put attapulgite clay into the above reaction solution, maintaining the bath ratio 1: 10- 20, after 1 to 2 hours of stirring, a colloidal solution;  c. Further putting a reducing agent, heating 70-80 ° C, precipitation of metal 4 on the surface of attapulgite clay and ^: holes; d. After filtering, dehydrating, and then baking with oxygen, the surface of metallic silver is oxidized to oxidized Ag ₂ 0, e. pulverized.  The method of claim 3 or 4, wherein the amount of the reducing agent formaldehyde is 20-30 ml. The method for producing a nano-silver long-acting broad-spectrum antibacterial mold-proof particle according to claim 3 or 4, It is characterized by the amount of reducing agent glucose or hydrogen peroxide being 60-80ml.  The nano-silver long-acting broad-spectrum antibacterial mold-proof particles according to claim 1 or 2, characterized in that it can be used as a filler for plastics.  The nano-silver long-lasting, broad-spectrum antibacterial mold-resistant particles according to claim 1 or 2, characterized in that it can be used as a filler for rubber.  The nano-silver long-acting Cantonese antibacterial and anti-mildew particles according to claim 1 or 2, characterized in that it can be used as a filler for architectural coatings.